■I 


( 


Digitized  by  the  Internet  Archive 
in  2016 


i V'-- 


https://archive.org/details/studyofproductsoOOcart 


A STUDY  OF  THE  PRODUCTS  OBTAINED  BY  THE 
SOLVENT  ACTION  OF  DI-PHENYL  ETHER 
ON  VARIOUS  COALS 


BY 

HERBERT  DUANE  GARTER 


THESIS 


FOR  THE 

DEGREE  OF  BACHELOR  OF  SCIENCE 

/ 


IN 


CHEMICAL  ENGINEERING 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 
UNIVERSITY  OF  ILLINOIS 


1922 


I 92^ 


UNIVERSITY  OF  ILLINOIS 


— ^fay-3-& 192-3-.- 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

Herb  ert- JDuana-Gajitar 

ENTITLED  ^ Btudy  of  the  Products  Obtained  by 
of  Di-Phenyl  Ether  on  Various  Coals. 

IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF Ba&helJDX--0-f-5.cl-enc.e 


In_  - Ch  eml  aal  - JE  n.,su.  ne  e j:  j 


Instructor  in  Charge 


Approved  : 


ACTINGr  head  of  department  of  _5HEMI_aTRY. 


r.  «iov5iA.u*7o  vfte>aiviKU 
r . k ..am  ^ I 


\ 


81  i^HT  3 in  rj.m  m th.tj  of  at  suIt  : ' 


i.  .- 

rw;^.j  ’■'  ' ■■“ 


-’■»•  ^ W ► . • ' 5'  ’ -»  jj ■ ; _- 

Iv.  ^ ^ ^ ™ 

<L  _T  -d 


1 r ^atrmpHjinAej. 


^3, 


.V^,-..=/ 


# 


1.  li 


m 


• ) 


i- 


I' 

tr^mt  t r^-  - *•:& 


i 


'isf?r ..  .1 . it%, UjijUiAiO^jzX.. 


'!  f\'  33iiufi^'nrv.d5J:jtA .:! V 
i ■!’. 

■ -■  ■ 


!»-  >■•  - ■M  * 


t *ir. 


rl« 


Jt  ■■ 


'1^ 


>-•%/»?  . '.  -■ 


1 crx 

. -•« 


'iL  '".--.tN 


^ HO  cia:-jh  otiTOA  ^■ 


f K iLr 


*w«esiS:^63sn»i^  r 


\r  ^ \ 


dt„  . 


k •« 


ACKHOWLEDCtMENT 

This  work  was  undertaken  in  the  Chemical  Laboratory 
of  the  University  of  Illinois.  The  problem  was  undertaken 
at  the  suggestion  of  Dr.  Laynd  and  its  completion  was 
due  to  a great  extent  by  his  kindly  co-operation  and 
advise.  I wish  to  take  this  opportunity  of  expressing 
my  appreciation. 


» 

■ ^v. , 

: 'V  •:■ 

■V 

7> 

.« 

., ' ' '■•  iT;’'.  'V;< 

/V, 


ii‘  V! 


__,.4*.^ ; . . ' /;  ;;£al  'I  . 

B:m  .eftXdfcrq  ^ 1 /^o 


rroi ft  ;qcr*«>ff  -.tl  ^'*t;  -p 


ii  '.V' 


.’■Ai) 


'•'00 


vtfj<|;iir  ‘>J6t!fT!:q  ^ 


*''  ysr^'»eA*^'ijlL!5  j ■ % ^ -<Niw  I ^ ftqivtx^--'^  :c5te4J,4a 

W - . ^ li'^r  ^ H w1 


. V 


'tifl  ,{l 

fi 


'•  € 


*.  -V,  ^■ 


sr<f 


■»  , . . W- 

,-v  V,'  ■ /. 


f I 


' ' a 


,V„  ♦ 


1 ' ^ 


..  j"*  *1*  V * , 


• ■ :>i\ 

l.'  «-  / v^.;i^)c^^l 


w- 


iJ^ 


We  ^>^1.  ■->  ^ '1 


'/f:  Jif  (7*^  ■ '*• 

Jh  'V 

Mi.  ■ !i  ■ 


' •»<ii 

. .,  ■■  A i 


r<? 


,Vi>.r  .lit  ' • iK  , 


m. 


A Study  of  the  Products  Obtsdned  by  the  Solvent 
Action  of  Di-Phenyl  Ether  on  Various 
Coals. 

1.  Introduction. 

1.  Nature  of  the  Problem. 

This  problem  is  one  of  a series  of  closely 
related  problems  which  are  be»ing  studied  in  this  labor- 
atory with  a purpose  of  learning  more  about  the  consti- 
tuents and  carbonization  of  coal.  At  first  the  compo- 
sition of  coal  was  studied  by  observing  the  products  that 
were  obtained  from  the  destructive  distillation  of  the  coal. 
Later  this  problem  was  attacked  using  solvents,  and 

much  work  has  been  done  along  this  line  during  recent 
years.  Various  compounds  have  been  tried  as  solvents,  but 
most  of  them  have  distinct  disadvantages,  in  some  oases  the 
solvent  acts  as  a reagent  rather  than  as  a solvent,  in  some 
it  forms  add  ition  products  with  the  coal,  while  with  other 
solvents  it  is  either  very  difficult  or  impossible  to 
remove  the  solvent  fromt&ie  products  obtained.  It  is  for 
this  reason  that  di-phenyl  ether  has  been  used  and  its 
effect  upon  the  products  observed. 

2.  Historical:- 

There  is  nothing  in  the  literature  concerning 
the  effect  of  di-phenyl  ether  on  coal,  but  a review  of 


t ♦. 


--T.rd^ 


'.-ah  ♦tf.'  lo  A 


■•ii 


:'~'-j(:  ''  ' ^OifeA  ■•( 
- ,-  ■ 


i :0  7jV •■T.t.Tl 


'4 


cr 


I'ii  ^ 


XAWtXr 


■^  ^ " -■•  rtforcj 

t.v  ’.  --i'jui  a.' 

'co^  .''  > 


"■■*'"**■  • : ■•?  i|;. 


■ :•'  1 


'.  C !• 


j ,r 


’.rri 


'Jv?  >1*.' 


■■tl  o.  ■ S./  _W  ^r- 

;■  * m'O'i  T : 


:;  - r '■;  , 


e:.'Tf  -V' 


: (r 


*:  •'^rr/ur''  - ; 


r of.'r  tiJTTC'h  '■•7' rfoVJl 


• >.  4*  ^ 

V V - . ' .’» 


V — 


HW»f^  i:  Tv- 

\ i:?o^  (ti:  , vfr.o 


^ • t :.Vi-.Ci  6-U.-.C.:  >’vv>iT;.V 

-^  • t.-rjv/ V^i  v/rf  meiff 


' T©rif*:i  f ■•:  , G.tox  -vloi 

V . ''  » 

■-  • '*.  .-71#,;  to; .*Ji;  €.'i»to1:  i’i 


■'  L • ifcc  7'.  I;,  r^' '.*:  Jr  ^?'bv  ::r- at  ^ 


rf-rev  ioe 


^rr.jJc^C  Sif-istcrt 


'.'cmz 


■ 7^;^■ 


''t  r:<*^'  VI  aiffit  ’< 

H 


r.  ^ 


iv ‘rv'f.'.^v,  - /fniTi;  s 


. .i 


r-  ^ 


j I ' 


ft  ► « 


isto.'.'cvo  VTift.--'  0?  J jC  ,..;^  at  V’tii*0[i  f J 

‘ .TV  -.  v'+M  I't;“  ^ .- 


OB^tQ  m 


I 


'.  ff  4 li  .'  \ 'r\t  4 


JDOfii 


-2- 


the  work  that  has  been  done  on  the  solvent  and  composition  of 
coal  problem  will  serve  as  a means  of  showii^  the  importance 
of  this  line  of  work,  and  why  it  is  desirous  to  obtain  a 
new  solvent  that  will  not  have  the  disadvantages  ^ich  have 
been  given  above. 

Coal  is  a substance  which  is  the  result  of  the 

degradation  of  cellulosic  constituents  together  with  resinous 

materials.  The  steps  in  this  degradation  as,  suggested  by 

1 

White  and  Thiessen  are  in  this  order,  peat,  lignite,  bitum- 
inous, and  then  anthracite.  l!?hite  says  that  the  earlier 
changes  in  the  formation  of  coal  are  biochemical,  while  the 
later  ones  are  dyn.amo chemical.  The  formation  of  each  variety 
of  coal  depends  upon  the  length  of  time  that  the  original 
plant  matter  has  been  exposed  to  the  physical  forces  of  the 
earth.  During  this  time  of  transformation  the  material  is 
subjected  to  heat  and  pressure. 

Ash  free  coal  consists  of  carbon,  hydrogen,  sulfup 
oxygen,  and  nitrogen,  but  the  coal  molecule  itself  is  very 
complea.  H9hite  has  shown  that  the  hydrogen  and  oxygen  content 
of  a coal  may  be  taken  as  an  index  to  the  coking  power  of  the 
coal.  It  this  hydrogen-oxygen  ratio  is  fifty-nine  or  more,  the 
coal  will  usually  give  good  coke.  Coals  which  have  been 

weathered  are  usually  poor  cokers  and  have  a low  hydrogen-ox^’’ga n 
2 

ratio.  Hobart  in  his  work  found  that  this  ratio  held  true  for 
the  coals  that  he  ^ed. 

The  changes  in  going  from  vegetable  matter  to  peat 


. . . V . ^ ^ ,,„ 

I'c  Aomuornco  a^ofc  ,(tj>ao  8^{f  4^  3f;io* 

■ '.s.  • , .•■■=■.•  . •■-  - . . . am.-  '■'",  ir^M 

• aon‘-:^2o<Twi  wJr  «rl^roi^»-  fsmM  h^^bb  iXtir  (roX^cncr ;i>>6o  . ;a 

j ^ "■  ,•  ■*,«_  -•-’  - ■■ . . ■ • J?  * >.  .-  ' ."  ! ^ 

' *■  rJ-Tdi^  of  siJOTtt^tl*  9i  ii  5>lri'  »k?^S5fXc^  11  ^ 


,1^, 


4r/  ^ evj/f  #oc  X£  Nf  Vc«vXo»  vec  '^h  * j 


•V? 


.^ircKl^  fffVlj  CfW 


1[.o  iki  <f!>i'  aoArf  miits  A et  'litoO  / 


riS  ''>*rJ‘^'' 


' ’ »tr 


,'’  .1^’ 


h.  ' ' '^  . . - . . 

- efciouf  ^i^r^oo:  of^oS^JCiaro 

.'"  ' “''  .t;.  ' I 'W,  ' 

, ''^  ''«*■'  ' s;  - ' '■  fi  . *»  '* 

4iaiulxi5»€  «s^/>.»' '•'^^i:^^iS^  .:5^i^-*XT3;tfiyr  **e»:t..,to 

. ^ ' -v  ■ ■;.  ; 

.’ ' Q.U  aXxfliw  tliJOlffiS-rfp-oXrf  6i/>aX^v>o '1^,^;  «Hlfe^■ 


V s&hu  v £foi;8  "'lo  noL’^ i «;» ol  *rlT 


^ - , '‘ft 

^*i0.'Atm9  r^fJU 

.,  .-■■■'.  .-  ■ ■ . ...  ■ '■»•'  ^V..  t '2  . •■'  ^' 

Xi'a>'i|qip.  wl?  I^  VtJSUitX  aii#  ii'fc'<^  ,££CWji^j& 

a 0''U*  ^lo  X/io  ^9'r^'fl^•  ntpif  tsc8>X<T' 

I ' 1 ’ -i  • ■ ^ ■ f*  * 

..*  . .,  / <v  ^ ,3  ^ «_. 

^ , r _.'  ...  K ■ ■ . .„.  , ' ’ . ..  ■ t - '.  M -< 

Z-  . ' ' 1 ’ »'i  . *'!{>•'•  if-'.  V’JH  . . j*c^. 

^ ,1-  ..'•^  5»  '*f  ts."  ,S» . , ti 

' ' - ' ' • ■ , / ' -''i '1 

tL'lXf/rj  ,c9^0'lti'xA  *^- - JvifB M900 '^XfjOo  vrw«Tfi  ^ 


■"■  < ' ji  (»  1 

, ■'■^.;va  A •T.fiaciw.  ( . 


f'  <(787/  ci  elvo€lon  X^cs  84^  iftJcf  tax  \n^^vio< 


Srso4rtt>C;,-i?^^  Xa4' fit" soft jjc4  ■ 

V .j«.-^  ■ ' '•■  'X'*  '■’  ' ^ " ■■  '^'  '■' 

■ xt?^‘t3fcX;  a« -fcjb  rt«a£|'i  04  00  & 

ari*  , ilk  >1  e Wijx  .?I ' '■  ■'.  Xa^e'"  ii 


\ tif  &d  iici  jfv  8 UoO  ^ .83ifw  60O8  ,TXle»iwi»  XXiw  Xipo 

■^  .:  . ,i  ,3  v.,'4v  ’ ; ■ ■ 


r eriT^o-nftjtyrtvrf' »oX  s ev!^;f  fenja  tnatirn  %Qoq.  aa/ fce^t 

' . • -P''.  *‘  ^\  •':  ^’••■''  'fi  **'* 

ZOt 


f *'*»i  *,»'2r  oiifjf  fcrtr.o'i ■ it C8T  airf  fit  ^x»cf«S  ■^Tc’iXj3X‘’g 

,V  •--  ‘ -c-i-  ^.'  " ■ ' ■^“‘J  -’"•^1 

* * ' ♦ ' * '^/li  ^ 

o ^ ^f!  tsto*^**  %oy.  oroft'*'  *j/i  tog,  a t aa '•  ift 

’'■’■■■  i - V--i-‘  :-’u'  :.'  ,:»^  ...  ■ 

, V 5» ‘'1^  i‘ilf-  -I  " * '*  - tW'^’  '.  '<’ 

■ - >'••  ■ -’■■  #-i  •-«  ' 


X"  s 

jaM 


-3- 


is  accomplished  with  a loss  of  water  and  oxygen*  The  changes 
in  the  coal  in  going  from  peat  to  anthra^cite  indicates  a 
tendency  to  approach  a hydrocarbon.  The  hydrogen,  carbon,  and 
oxygen  come  from  the  celliilosic  part  of  the  vegetable  matter. 

The  nitrogen  comes  partly  from  the  animal  matter  which  is 
included  with  the  vegetable  matter  and  the  remainder  from  the 
plant  substance.  The  original  plant  and  vegetable  matter 
tooth  contain  some  sulfur.  This  gives  use  to  the  organic  sulfur 
in  coal.  Other  sulfur  compounds,  chiefly  iron  and  calcium, 
are  formed  from  the  hydrogen  sulfide  waters  that  percolate 
through  the  coal  and  precipitates  insoluable  compounds. _ The 
iron  and  calcium  compounds  usually  form  most  of  the  ash. 

The  constitution  of  coal  until  the  present  time 

has  been  studied  almost  entirely  from  the  basis  of  destruction 

distillation.  This  method  is  a poor  one,  because  it  does 

not  tell  the  real  nature  of  the  coal,  but  it  has  been  developed 

on  account  of  the  great  commerci  fJ.  importance  of  coke  and  gas 

manufacturing.  The  products  from  such  a distillation  are 

the  decomposition  products  of  more  complex  molecules  and  are 

divided  into  gaseous,  liquid  and  solid  condensate,  and  a residue 

3 

which  consists  chiefly  of  carbon  and  ash.  The  volatile  products 
consist  of  ammonia,  carbon  dioxide,  hydrogen  sulfide,  hydrogen, 
methane,  carbon  monoxide,  nitrogen,  acetylene,  ethylene,  other 
hydrocarbons  / pyridin,  phenol,  benzene,  toluene,  xylene,  naptha - 
Isene,  anthracene , .phenanthrene,  cresol,  and  a great  variety 
of  aromatic  compounds.  The  presence  of  a predominance  of 
ring  hydrocarbons  and  their  derivatives  had  led  to  a belief 


I 


,'  ' ‘■•V 


-T-’ 

fK 


r'i'*'l  V ■Jip  M»OX  r 


■ . vl 


*,■»  r 


• *. . -'O  C:i;‘  . ‘ 

•- 

ti  hK  ‘ iij;  « ,t t / ■;.  - 

s, 

,•:?•■••  i , ii ■•  '*/  .'  .<? 

; :.  i t.!.:-  * " -.v  . ; g 

ci  ,*:  ‘ •■/.^.  ;ti  L 'K  r;,-  ■ 

'>i'\t  ■■  •'  . '"iiU.''.  i .'if.V  ‘ r..  j.',  ':■  I S ' ■; 


^ ~ 


0\ 


ut  ^J: 

■!%*'•'-  JftO? 


j*«i  'VVy  *• 


. r ••‘100  1 '••;<?'  '; . 


V 1 ■■  ' CV  : .;  ■ '•  ■ 

■’  • .“■:  - *■  7 ' ■ ' • " Tf'.- 


'•>>  Ui:  i'.r 


*.  . r ..r. 


c» 


■ r, ' *• 


• 7.  * ‘r  ■■&:•;! 

• ".  ^sj  srf^  - V 


' ' / '.  i;f* 

•.  f(‘  . '!■,.  ■'•  • • ■ : 

I ' 

•''Ov'-u'r-  iv.  • 

‘ 7-,  '*  ■ 


’.  ' .7 >7  1 

" . '0  e-c 


•o  ' sir 


. • I ‘ r 

? ' -r. 


^ * •^ir*  ^ T ' 1 V;  ^ 


4.  . * . ‘ , 


X '.  -'■  r”  j 'i.  Op-  ' '-■ 

j- :'  - .:  • .. : , L * 


#4  b#  ^ 


i.  i<i^  .<■ 


. . . ♦ > * 


■ ; r 


7;.  I,  OX 


riO:.'«v  ; 


■ tp.'fi  *■•■,' 1* 


‘-7i-  . ' : /.  or  :<o 


iM 


fe  .■’f . 


■'  'OP  ''  ' Tofr  1 ■-.'Otr*-  ^ 


: 'XX  ■ no: 

r ’oo„'  n-'; 

. , r>rl 

.1  -fe 


.'  loo  •it/T  , pr'C'T^o  e.,  n--,  . j/.. 

. 'f. -^,c7*.  :4-f- , i:':  r w.'  i ••: -0' .-*,  . niOiT^i  '.■  ' ':c<xoo 

70  ..p  -livr:  ^o:r  :;n'  , .'o::  ^.r;  ,7'r  r'  o^  , raccf 7''-ocn ' •.’ 

P.-Sfr'js  i -*‘T/  , roAO';  - ; -n.'ti:  . : ■'■  •■  •. 

-o  fcr  / .-i:0oii5  7nr  ' •>  '>ro:oOO:cr  ti7  , o 

A 0^  / nr{  0 : . L,^.vX:5©fc  .,i;  onoiJ  ;a.  oo.':^ya 


- in: 


if. 


'b.'oTx,' 


-4- 


that  the  coal  consisted  of  ring  like  compounds.  The  work 
that  has  been  done  on  the  destructive  distillation  side  will 
not  be  discussed  inasmuch  as  the  work  is  almost  entirely  a 
study  of  the  volatile  prodnopts  from  coal  and  does  not  involve 
the  use  of  solvents. 

Another  method  of  attacking  the  constitution  of 

co^l  problems  is  by  the  use  of  solvents.  This  has  been  the 

basis  of  much  investigation  in  the  connection  with  the  coking 

properties  of  coal.  Most  of  this  research  has  been  dons 

on  account  of  the  commercial  importance  of  coke.  A review  of 

the  work  along  this  line  follows: 

4 

Reinsch  in  1885  conducted  some  experiments  usirg 
solvents  on  coal.  He  concluded  that  by  means  of  solvents  it  is 
possible  to  i^solate  from  coal  substances  \iiiich  are  quite  amor- 
phous, do  not  exhibit  signs  of  organic  structure,  and  which  are 
characterized  by  their  resistance  to  concentrated  mineral  acids 
and  atmospheric  influences.  He  is  of  the  opinion  that  coal  is 
composed  of  two  substances  which  are  distinguished  by  the 

difference  in  their  behaviour  with  alkaline  solutions. 

5 

in  1898  Anderson  and  Roberts  said  that  caustic 
potash  afforded  a means  of  differentiating  coking  from  non- 
coking coals. 

6 

Baker  used  pyridin  having  a boiling  point 
o 

110-130  C.  as  a solvent.  The  percent  extract  varied  with  the 

kind  of  coal.  The  highest  extract  was  30.4  percent. 

7 

Later  Anderson  and  Hend.erson  treated  coal 


-5- 


in  a Soxhlet  with  pyridin.  They  say  that  the  carbon,  hydrogen, 
and  nitrogen  in  the  extract  are  similar  to  those  in  the  original 
coal,  although  the  carbon  is  usually  less.  With  inferior 
coking  cords  they  found  that  the  treatment  with  pyridin  destroyed 
the  coking  power,  and  in  strong  coking  coals  the  coking  power 
is  impaired  but  not  destroyed.  The  amount  extracte  d was 
from  15  to  21  percent. 

8 

In  1908  Bedson  and  Blair  used  pyridin  as  a solvent 
and  obtained  an  extract  that  varied  from  22  to  32  percent.  Bedson 
used  pyridin  which  gave  as  high  as  20.4  percent  extract  on  cer- 
tain bituminous  cords.  It  yielded  extracts  of  from  dark  red  to 
brown  color  and  in  some  instances  it  exhibited  a green  fluores- 
cence. The  undissolved  residue  from  the  extraction  was  almost 
devoid  of  coking  properties. 

9 

In  1912  Lewes  gave  the  result  of  his  investiga- 
tion using  pyridin.  There  acre  twC  different  resinic  bodies 
present  in  the  coed,  one  is  easily  oxidizable,  soluable  in 
pyridin  and  saponifiable  with  alkalies,  and  which  upon  weather^ 
ing  is  oxidized  into  humtus  body  with  the  evolution  of  wa.ter 
and  carbon  dioxide  and  is  responsible  for  the  heating  of  coal 
ain  storage:  the  other  class  non-oxidi sable , not  saponified  by 
alkalies,  and  forming  with  pyridin  a compound  insoluif.ble  in 
excess  of  reagent,  and  this  class  may  be  hydrocarbons  from 
decomposed  resins  as  the  residue  in  which  they  are  present 
yield  rich  liquid  hydrocarbons,  as  tar  and  pitch,  but  are  not 
rich  in  gas. 


5* 


t ,' 


“a>o  ©f.’:  ’ 


7 V'?  4 


^ I 


M 


■.vr  f . 


r i Ju.a-  ft  r*  t*  ' ;.** 

.^'  • • : vX'.  .'•ci;  ». 


yZ  .^*•  - ■ .^;  2i  "•  I ■ y - fi  -T  ' ; : ■,'.  -■>  .t  ■ ^ (•  f .t 

i ..  * ";•  CJC.  't  ; 


TO'Tv  a 


■V'l  I 4^ 


" v-/'r 


'0  :;r> 
r.'  : ■ ■ ' :::*i:i 

, r+'  ' • 


' ^ i j . c ^ . . 

,'  6 ■'  <,  i 

r ^ r,  •■  ^ >*n* 

- fc.  Uw  .*  T 


■l"  '•  UiV!  aoefc--;  c<"::  ., 


:;::  ot  ac.'iTV.'^ 


. \'  ^ 


■*  > 


Q iinx. 


'•  i ."j  4^  p; 


O p: 


^ f'' I ' ^ ‘ ‘ I •.• 


ci'-tl  VL  ' ■ ^ 

' 

I",  f -.>-  ^tL‘-k»r^ 

* • ' -1  *^s  4. 


C -1\  f. 


W ^ t ^ . -V 


i:l 


r f“  r o r 


/ . I .. 


On? 


■' 


* • i,  w 


ji  ''  ' •--■ 

. } A'  ■ .-  . 4 r 


vi:  :i/  ■■■,-'■  ‘ . 

-.0  r: 0 - •:  :/■' V • . . r 
I. ''  ')^-  'C  'I'  ' - , ’’  ■ ' 


. "•  : TC7.r'9  ,| 


il 


s 


; . ■ ' f '.'NnJ  : f-.i 

r ' Zy'.  ’*!!',  '•••.*  '’•?  -o 

' 1' ■ , Xo  r.Ovf^p  ©i  • r ■ *:;0^H 

'■■  ' - rq  i{.r k.x  1 *-.;n  loli.  ‘ " , 


I' 


■t  D5:;  . *' 


'r  ' • 

u, 

.40J*q  jfc.vt 

■■-'''  i 


">j.  ^ '■  ^-,’C  0 ■ 


^ Cl  rk  t^ 


''■'U'  .■.;::A5:1 


^•  ' r ■’•  - 


-6- 


10 

Dimroth  and  Kerkovious  used  nitric  acid 
on  coal.  The  residue  from  this  extract  was  a.gain  extracted 
with  ether  and  gave  a substance  which  was  amorphous  and  hygro- 
scopic. It  gave  a black  color  with  alkali  and  was  easily 
soluable  in  alcohol. 

11 

Pictet  and  Ramseyer  used  benzene  on  a "fat” 
French  coal  and  obtained  hexatiydrofluorene  together  with  some 
polymers. 


12 


Vignon  used  aniline  on  different  types  of 
coal  and  obtained  extracts  which  ran  as  high  as  35  percent. 
He  also  used  beta  quinoline  on  a "fat"  coal  and  obtained  an 


extract  of  47  percent. 

13 

Fisher  and  Oluud  used  benzene  under  pressure. 

o 

The  extract  which  was  6.7  per  cent,  would  soften  at  140  and 

o 0 

run  at  180  C.  Cannels  coals  heated  to  350  with  naphthalene 
and  extract  recovered  with  chloroform  in  a Soxhlet  gave  a 
yield  of  35  to  30  percent.  They  also  used  liquid  sulfur  dioxide 
to  extract  the  coal,  but  in  such  cases  the  residue  was  very 
small. 


14 

In  1912  Wahl  used  pyridin  in  a Soxblet  and 
obtained  as  high  as  25  percent  for  the  extracted  material.  The 
residue  had  poor  coking  properties,  but  if  the  extract  was 
added  to  the  residue,  the  mixture  will  produce  a coke  similar 
to  that  of  the  raw  sample. 

15 

Clark  and  feeler  extracted  coal  with  pyridin 
and  then  the  pyridin  extract  was  treated  with  chloroform.  It 


.-Zi  IT  ^ 


’m- 


'i'-'fl  'Jifi 


1. 

.<?»>»  .-.  -’ 


- '• 

* V*'. 


'..  ■ oi  a-  -. ' „ . 

■'  VfclcH  '^o  il  .*'.  \ / 


■X  , ;:  X ' ■ '■'  ■'  ' • ''”XL  ■ '■ 

cMSoJ  0My>  to^'xifxe  wlrt  jjdipB, . 


5 [>  i;~--  6imd<r-cynt  d4if  ,rf0ittv':  ^Q«4;fwV«  4 ev^ 

•'■3^.'  -.'■“.■  i|.  "•  ^ ■ 

i \n0jL9  nJTtr  *Jinr4  iXniiijl  TOlo»  itsiAJLif  * flf. 


ft.  •»! 


i;X 


,lodGQifi 


',■>1 


I 


■f. 


» »>■ 


eitwe  tv  ^x»Atr  ?f>:!>  ^«®trc<rt‘I^^!iTfd’Xs=d  i>jf  fcijji  doftftT^,  - 

^ '•  • '■'  ■ ■ .,•  • .*,"  1 i.  '.:Q  "■ 

'%  •'-'••»■  *“1 


\<t  v*!jqx^  i» 


■^r  ■ ^ 4^  / ;■  ^ ‘-<t!S[a*aY405[,>^ 

^ 'ir  « . '■.  ^ ^ -V , , ' 


(toaftl^ 


i ^ ffjs  ^!.acd  rfc?  - tc(  #i5-|i9  ^'fc4MrXt'irfo^fc«x 


'‘’:ai  t<kii^ftio^btt^  t/.'O  » 


n. 


, brx  iijdtXi  !-mip  .^, 

,?*'  0^•C  do  Ilf*  ^oxtiste  edT 


Jr'i  V ***'  -t  ''''  "•’**■  '>■'«'  • '•  ' 

■'Vr^^fMtdcy^iin  d'K-ir  X>GF‘  'dlxo.-j  ',*t5  .Ool,;  am,-  ' , 

•?  ■•  1-  ;•  •>  '••  i*!  . '-W-  • B'’ 

■ . . ' • ..  '-...T>  ■ ' , ''V'-;, ’ , c-  ';_,>  fifti/'Z  ■" 


’mfiifi  -iutiim  htV(: f<£.  iB«ff  V^,,nit^.  ?.  ',ioo»<l  Ot  Hi-  »S,  ’.T-j 

' : . ;'*^-5i9'.  '"  ,y  '-  ■' •■;'  ■'h:;.''l'/ 

..,♦,.1*0^  cit*  ,a.’i^l50x  .•at^ae  al  >■  m 


- 


^1 


. Xi^ji 


:^Xrb:o<9Jv  xr^  -7  I’ljit  SX^X  fli 


‘:i' 


-53T 


if  sdjf,  o,4/d|id 

r.j  r ,,]  ' '■^-  ■•'''■»  f •-•i  '"'  ' 

’ ■ '‘^■'-  V.:  '’'  (siL'l  ......r'l’'^ '"’hh^i 


. .rXiitlT  oioo  r;  EX)^  *1^?  ^ •dJf  ^df/Jble  ni  ad^  o*f 

.t  IqgUiB  yrjt’t  dtU  <?^ 


alblrxQ  dtlt-r”  X;oar!^>^.oti^X'5  xalaadT  J?r»  ^li^XO  ' •.  > 


.mao^cwolrfo  diiw  tf-6$%tX9  dd.^^ft'^dAf 

•.i  ,..*  ■'  VSit*.  - ■'  *.  i.‘"  ^ r j 


1^4 


irsds^.  . --■^ 


t- 


-7- 


was  noted  from  the  ultimate  analysis  that  the  increase  in  the 
amount  of  nitrogen  v/as  3.75  percent,  showing  that  nitrogen 
had  been  added  from  some  source. 

16 

Frazier  and  Hoffmeji  using  phenol  forund  that,  some 
of  the  substances  isolated  approach  pure  compounds,  and  some 
appear  to  be  quite  pure  hydrocarbons  containing  small  amounts 
of  oxygenated  compounds.  The  investigations  was  to  be  con- 
tinued using  pyridin  as  the  solvent. 

17 

Parr  and  Hadley  usir*g  phenol  say  that,  (l)  Extrac- 
tion of  coal  leaves  a residue  that  will  not  coke.  The  coking 
constituents  of  the  coal  is  in  the  extract,  (s)  Destructive 
distillation  of  the  residue  and  the  extract  gave  practically 
the  same  gases.  (3)  0xid3.tion  of  coal  residue,  or  extract, 
produces  a lowering  of  the  percent  of  \^olatile  matter.  (4)  Ox- 
idation decreases  the  amount  of  material  that  can  be  extracted 
from  coa.1  with  phenol  and  the  coking  properties  are  decreased 

in  proportion  to  the  extent  of  oxidation. 

18 

Later  Cherry  working  on  the  effect  of  oxygen  on 
coal  and  the  subsequent  effect  of  phenol  on  the  weathered 
coal  found  that  the  cellulosi*  portion  has  greater  avidity 
for  oxygen  than  the  resinic  portion;  the  effect  of  oxygen  on 
the  cellulosic  constituents  is  sufficient  to  destroy  the  coking 
power  of  the  coal. 


/ ' _ ' • 

arr--r^ga3e.'a: 


-‘  ■' 


I’  . '•'  . . ’ I»|'* 

• l.  ' » , ' 

* fit  >4l  4-  tTi  tl^ 


'SU 


I 


- ^ >u  ■ ■ p' 

02?  '^040tt^Si8»^  ;' 

K’"'  -V  * ' V ■ ^;^..  jf  ■ 

^ -;i. ' L^o*.  tii*t  njj^n  «wflT.  >.2it  ,lro 

V ‘v'  ■ ' • "'■ 

. ‘'-  M^v-''  V " \ ytyp^<nr.  i.Vv.i.'i^'ei^i,  tir  fii;t£i! 

it  «r>?s  f>aiC7®'2  £joa 

aiHO*  I n -^Lffurocpioo  ^24ira  ’,8' 

,Viv>i-yn/?''*IX*anil  TTiTtiiifttAc*  A«iod2jeorrUM--«Tt..<t  o^' 


^ iJ[  ^ni 

-/Tdr  6tf  of  ^ f£lo2f4^t^|3jlSl^2 

^ * A*  ^** ..  . It  '« 


»•’<  '.  •■:  • » ■•‘-  -'M«--WA.‘ 

Ab/  ~0A:rt'Js5r fX}  , Xcsr..t4<i  :^X»iW  *«  TbrT?  AvA  fc'i 

■ ^ ^ -lM 

' A.rijfoo  ejcT'  tOA  Ii.^  iJ  V9Vr»X  XiiCO 

' , ■ - -•  • ■■*■  ^ 

©VUOW?l^t-<^  (•■^y  t f .,0c-  -o/:  ’'c  CXf 


P'> 


* r 


^'ViX4‘Ci.fo<rJ<r  '•,.‘«'^^i.  • •''-*  b%,' W ■^,^*''ia:ci,f«tf'i^ 


t ?o  4^:  Ij’Vi  X^uc-  1:'  i?)  . eaa^ 


■' -^Q>(|) 


^ I 


;li^^5^:>1f^u  w 'itifed  'U  f4*jQiih^  •■■  rffTT*e«4#l<swif)*vioif^ 

**  --••-■  -.n;  :>}j  i/,-  ' 


.iV 


FV'i  j 'S ' ^.t.4oo' 

Ih-'.j  jjit  * ^'-  ■ ’ ”••  ‘^*5'S^Vi*^Xjp'£^,lo  .*rr'^fjc«.  of  xii,.  .J'-.’ 


<1 


'1  r 


j '-'iso  ’-r t- f- J;;  •/-  J 

1 '■'5.'^^'  «vf;t'i4S0  ‘ 1 


‘"I  V,,.^'  ' .•4  ■ 

- ll  ■ ■ •■  ► jL  i<--  ‘ *.•  >■  ■ tf.  ' •■  ■ , . ■ I V '<;  — '•■^  3 f 

Tr  f .-  ...  .^  . ■'  ■ <‘  <-.  ^'  i,<  ..1  . , , , , ■ V.V-.w  '»  ■ , ' IB  ■»,.'. 


, T^  ■ 

«. 


' IT  ^ ''■^V  *\ 
#>■ 


f-  : ¥ 


' -k 


S 


*.r4) 


/■  V.  .-.''A©?/!!  il 


r'/'  -a 

'Ar'M 


V& 


-8- 


II.  Experimentcil . 

1.  Apparatus. 

The  extraction  was  conducted  in  an  erlenmyer 
flask  with  a long  refiiuxing  tube.  The  end  of  this  tube  was 
connected  to  a trap  containing  alkaline  P3^ro gallop  in  order  to 
keep  oxygen  out  and  thus  reduce  any  tendency  to  oxidize.  The 
flask  was  placed  in  an  electric  furnace  where  the  tanperature 
was  controlled  by  a variable  resistance. 

The  excess  of  di-phenyl  ether  was  distilled 

off,  and  the  extract  finally  dried  in  an  electric  furnace 

in  an  apparatus  as  shown  in  Figure  1. 

The  apparatus  used  in  all  of  the  carbonization 

tests  is  sliown  in  Figure  2.  The  apparatus  was  swept  with 
200  oc.  of  nitrogen  before  and  after  the  run. 

The  extract  and  residue  were  both  dried  in 

an  atmosphere  of  nitrogen. 

The  extraction  with  alcoholic  potash  was 
carried  out  in  an  erlenmyer  with  a water  condenser  on  a steam 
bath. 

2.  Determination  of  products. 

The  ultimate  analysis  was  made  according,  to 
standard  methods,  and  the  gases  from  the  carbonization  tests 
were  analyzed  in  a University  of  Illinois  modified  Orsat 
apparatus.  The  results  from  the  ultimate  analysis  are 
checked  in  tables  5,  6,  7,  8,  9 and  10. 


li 


''TSf 
T'rjV 


7: 


II. 


SfT 
■ • 


'■Vf 


• '»Vi 

■ *v  V 


'.  . •' A' 


•■  :t:. 


vr"  3nt>jt /a  # • V :f*jsXV 

- 's/  •■■'%•) 

;■>  * ■ ixi  s n>f  ■-■  L'>  > n ;^rr 


» ' V f 


,7e/>  Tv,  'u.  i?i  r>'  v/.w  £1 


■ft  *j 


*^-.  ’r.y  X h r .'■''lifiiod- 4iHr 

♦**»-■' 


r 


.v-<» 


,'rv,'  '.<>  c 'i: 


-Jl  f) 


1 r 


^w-j  f:. 


' ■ r 


, 1 


rc  1 


ooe 


-.  X 


./ ♦ f ■>  ■:■  'i-7.-  c-^r  ?7 ^ Tr 


3 ’. 

Vv.t^.' 


:>  ■ - : ;v  ' • , r v » _r:  ; . . ♦ 


.‘:^  xe  ak  :l  f'h>2  \'  ' .'  r' 


\ 

• * 

r 


.j’r.-'j  d'cr  ; > <ici  f£t>^ir':f 


) ' 


•,  1 


<^  , ytfivr/^  rtw  ^o /%.  i''/tr/to  *fj^^'/ 

/?.  /»i^/!f/^/ic  /5<< . 

C-  tj  ty  ^ i,  . 


i 


1. 

H 

'% 

X 

« 


<l 

t 


')J 

'2 

V)  ^ 


> 

s \ 
W ^ 


V' 

5 

V) 

I 

Q 

V5 


0 X 

^ 'I 

X < 

? ^ f; ^ ^ ? 


i 

A .'» 


\ 'a 

^ V> 
>) 


'4l 

>1 

W 

\. 

0 

V 

0 

V 

'I 

S 

I 

n 


^ o P tJ  y. 


I K “>  Jj” 


-9- 


The  tar  given  off  was  so  small  that  it  could 
not  be  separated  from  the  water  that  condensed  with  it.  The 
water  that  did  not  condense  with  the  tar  was  caught  in  a 
calcium  chloride  tube  and  weighed. 

In  the  carbonization  tests  on  coal,  the  hydrogen 
sulfide  was  determined  ty  finding  the  increase  in  weight  of 
^he  cadnium  sulfate  tube.  This  method,  however,  wqs  not 
entirely  satisfactory  so  in  the  later  runs  the  cadrsium  sulfide 
was  filtered  off  and  weighed,  and  the  am.ount  of  hydrogen  sulfxLe 
was  calculated  froi$  this. 

3.  Types  of  Coal  Used. 

Three  di  "^^ferent  coals  were  used  in  effort  to 
observe  the  effect  of  di-phenyl  ether  on  coals  of  different 
character.  A fresh  sample  of  Franklin  County  Blue  Ridge 
Cool  was  used  as  a sample  from  Illinois.  The  Inaiana  sample 
was  a fourth  vein  coal  about  four  months  old,  while  the  Alberta 
coal  was  from  the  Canadian  Pacific  Phtilroad  mine  4^14  and  was 
about  one  year  old.  The  coals  were  first  extracted  with 
di-phenyl  ether  and  this  residue  extracted  with  alcoholic 
potash. 

III.  Results. 

Results  of  all  the  analyses  are  given  in  tabular 
form  in  the  following  tables.  In  tables  5,6,  7,  8 and  9 and 
10  the  value  in  the  fifth  column  for  the  composition  of  the 
extract  is  obtained  by  calculating  the  amount  of  each  const ituoit 
of  the  original  coal  that  should  go  into  the  extract. 


■'  , o*:  .'o  • ' ' : o nl 


i 

' '-  .-■-*;  ‘1.-  ^ ^ 

■ 4 

i' 

1' 

1 

' t ' • * -Oit» 

j ■!. 

■ •■ 

»’ 

K 

'*  -■ 

- i 

( > 

i 

! 

1 

- j *jL  £ Kji*  jTrl  C".  .r 

-K-  >3 

\ 

1 1 ■ ' 

i 

4 

-'  ■•  \0\  ‘ .'  n ‘•"1  ' ■ ,,.'  ■• 

V'  '7  "'r'^  «iitr 

!i  ^ 

. i 

( 

-^;;i7‘':  '.  '’j.‘4»c  Q^'V; 

'i; 

1 

) 

_ 

~^«i»  f-  t ^ 

*7 

^ • . 

i:  ' 

’fe'j 

^ 

i 

C*'  :.vc;0  V*  ••v^  *>' 

1 ! 

i 

'■  ■’  ^'-  ' " --i  £-:'-V  • .*T.-  £ ' -■  ■- 

1 

1. 

1 

O ' '.;rx*3acro  ,i 

•,! 


J 


t 


- > 


t . ■ ’ . ■ 

* 


' 

' ' *'  6l‘,in**i  K V *’v-7.i'T/ '*■  {acr'i 

• ~ r ■.  .1  . - . ;.  'X3'  ’ 

' !,n.r 

I • ' 

■ 

' . j ' . ’ » 

t- 

■ ■ V 

■^OYr;,;T-.  „;t7  ^'li  ^ 

Tjf'Xfij'  * '■•  ^ tvcrrol 

- i*  ■ 7 .'  L . i"  :,>i.^  r-'  fi-j 

^' • ‘.v'i?.'  f ^'  '^’Siiti  '"v-z  1j  r ■ :t:- ■- 

■ i I ^ .'  '!'!:  iffppf. 


h 


I H 


Extraction  of  Illinois  Coal  with  Di-phenyl  ether. 


/linount  of 
Coal 

Amount  of 
Solvent 

Time 

Temp,  in 
Furn  ice 

i-  Extract 
of  moist, 
and  ash 
free  coal 

60  grs. 

300  grs. 

34  hrs. 

0 

330  C 

3.16 

10  ” 

300  " 

30  « 

0 

350  C 

3.39 

10  " 

300  ” 

6 " 

0 

360  C 

3.39 

o 

CD 

300  ” 

48  " 

0 

350  C 

3.85 

O 

CO 

390  " 

00 

0 

330  C 

3.85 

O 
1 — 1 

300  « 

30  *’ 

0 

380  C 

3.85 

Table  I. 


I 


srr-  ?:::=;:« . ( |^ 


r^Ttr.^*  Mr  - pi  ■■ 


'-ir;.-’ 


: r.l 


,„■  J 

i?l 


‘:,"  ■' ft 

' ' -■  V ;,\j7 

...V:/ 


.UpO  blwrt^i^o. 

1.  ■ , . "j;;.  . 


. - .icftf  S»T«o .’ 

tv-.vf--, 

ti^CP 

•i»K=Jfc^r^  ;-r-^oiS»fcs=3t 


ViA  4C1»  V..fc.<jq,V  «, 


- ' ■ C^' 


? 1 j It:: 


« v:  ■ 

■ <*  t ' 

0 OCi'  -'-'t.  .i'>4.*^  j .ft,?:?  cdf- '.  p„  ■ 

o '.!  V -.‘5 

' ^ \,  m ^ 

( . * ■ ' I “ ■' 

':  'J  \ -'  " . 


■•  y( 

V CCS  fe  • ' M., 


b' 


ST’ '■'■'■ 

A' 


:?  ; . 


■ yi. 


^'■'ii^j^-%%'"^ 


- llu>'JV»  . A 


f' 

\ ^r-  :i 


L 


, P>'  ''•' 


• ' «CS  .*  ■^;^fC)^  ;'' 


V ■ .^,  ;.  . / 

, -I-  ■ r-----  ■.,  - 

I ^'  ' <^  I ' •'  ^ 

— — .— ifc  ^ »*^**-  » I '■  *♦  ^ "“*'**1^'**'"  *•  ■♦■  ij^i!^^ <1^  I'A  f 

4 ^ ■'’  .^;:  ■ ''Iviv  . -\y 


*'JU 


m 


. C05*.  I K.-'  6x;j 

.••jJ  ■•  j»r-  *■  ' >»^  ie'*  *^y 


v;. 


■ * • • 


>4.' 


/ .,A 

‘i'rP-M  ft. 

< ,la,'rw 


<(M|  • 


f,  ! 


'‘A 


„1L "'i* 


Afti*  V *-■ 


r ,’W‘  -*♦*•'. 

■Ai  ^.W.i 


Analysis  of  Coal  Samples 

Illinois 

Inciiana 

Alberta 

Air 

Dry 

Dry 

IM  & A 
Free 

Air 

Dry 

Dry 

M & A 
Free 

Air 

Dry 

Dry 

M & A 
Free 

Air  Dry 
LO  88 

3.  33 

- 

- 

4.76 

- 

- 

-0- 

- 

- 

Mo i st . 

4.03 

- 

- 

1.66 

- 

- 

.68 

- 

- 

Vol  .Mat 

34.85 

36.31 

39.  39 

43.52 

44.25 

48. 79 

15.78 

15.89 

16.76 

Ash 

7.50 

7.82 

- 

9.17 

9.  33 

- 

5.22 

5.25 

- 

Sulphur 

1.31 

1.36 

1.48 

3.75 

3.81 

4.30 

.76 

.77 

83.74' 

.81 
^ 88.  30 

Total  C 

t 

6$.  85 

72.78 

78.95 

70.67 

71.85 

79.23 

83.18 

Hydroge: 

1 4.67 

4.87 

5.27 

5.03 

5.12 

5.66 

4.42 

4.45 

4.69 

Oxygen 

11.09 

11.56 

12.53 

8.  32 

8.47 

9.  34 

4.29 

4.  32 

4.55 

Nitro-r 

sen 

1.55 

1.61 

1. 75 

1.41 

1.43 

1.58 

1.46 

1.47 

1.55 

B.T.U. 

12774 

13309 

14437 

12S01 

13118 

14465 

14641 

14740 

15550 

Extract 

3.5 

3.64 

3.95 

5.  44 

5.52 

6.05 

.5 

.5 

.5 

\ 

Table  2. 

, 5- 

Analysis  of  di-phenyl  Ether  Residues 

Illinois 

Indiana 

Alberta 

Dry 

Ash 

Free 

Dry 

Ash 

Free 

1 

Dry 

Ash 

Free 

Vol.  Mat. 

36.  73 

39.98 

49.41 

5 4.15 

21.  72 

22.90 

Ash 

8.15 

- 

8.76 

- 

5.27 

— 

Sulphur 

1.09 

1.18 

3.98 

3.26 

. 75 

.79 

Total  C. 

73.37 

78.  78 

73.83 

79.83 

83.  30 

88.31 

Hydrogen 

5.76 

6.38 

5.00 

5.48 

4.71 

4.96 

Oxygen 

11.11 

IS.  10 

9.10 

9.97 

4.07 

4.  29 

Nitrogen 

1.53 

1.65 

1.33 

1.45 

1.44 

1.53 

B.  T.  U. 

13107 

14369 

i 13064 

14314 

14828 

15643 

KOH  Ext. 

6.51 

7.09 

1.64 

1.80 

.12 

.13 

Table  3. 

1 t 

V*'  * !'^*''V^^  '‘^’>-'- 

• •■.  ,-V  .t 


'/pr.i  y 

*#% 


rr'  " 


TjrU  . 


r 

\ 

i. 


rr,. 


I 

f 


f 


if. 


Analysis 

of  Alcoholic  Potash  Residues 

1 

Illi  nois 

Indiana 

j 

Alberta  | 

i 

Dry 

Ash 

Free 

Dry 

Ash 

Free 

Dry 

Ash 

Fr®e 

Vol.  Mat 

34.55 

34.96 

34.93 

46.56 

17.16 

17.56 

Ash 

6.53 

- 

24.99 

- 

2.  32 

- 

Sulphur 

1 .35 

1.  44 

2.94 

3.92 

.72 

.74 

Total  C. 

74.64 

79.84 

58.  40 

77.84 

87.  70 

89.78 

Hydrogen 

4.66 

4.-98 

4.64 

6.19 

4.21 

4.31 

Oxygen 

12.62 

13.50 

8.02 

10.69 

3.96 

• • • 

4.05 

Nitogen 

1.21 

1.29 

1.07 

1.  34 

1.09 

1.11 

B.  T.  U. 

12834 

13728 

108  72 

14492 

15087 

15444 

M 

Table  4. 

1 

Balance  Sheet  for  Illircis  Coal 
Di-phenyl  Ether  Residue  to  Coal 

Ash 

Free 

Residue 

To  M & A 
Free  Coal 

Coal 

Differ- 

ence 

Amount 

of 

Coal  to 
Extract 

Error 

Ydeld 

96.05 

3.95 

Total  C 

78.78 

75.68 

78.9  5 

3.27 

3.12 

t .15 

Sulphur 

1.18 

1.13 

1.  48 

.34 

.01 

/ .33 

Hydroger 

6.28 

6.03 

5.37 

'.76 

.21 

'.96 

Oxygen 

12.10 

11.63 

12.53 

.91 

. SD 

41 

Ritro- 

een 

1.65 

1.58 

1.75 

.17 

.01 

^.16 

B.T.U. 

1426R 

13705 

14437 

732 

570 

^ 162 

Table  5. 

■ 

Balance  for  Indiana  Coal 
Di-Phenyl  Ether  Residue  to  Coal 


Ash 

Free 

Residue 

To  M & A 
Free  Coal 

Coal 

Di ffer- 
ence 

Amt . of 
Coal  to 
Extract 

Error 

Yield 

93.95 

6.05 

Total  C 

79.83 

74.  89 

79.33 

4.34 

4.79 

-.45 

Sulphur 

3.26 

3.05 

4.30 

1.15 

.35 

+ .90 

Hydroger 

5.  48 

5.15 

5.64 

. 49 

.30 

+.19 

Oxyg  en 

9.97 

9.  36 

9.3ft 

- .03 

.56 

58 

Nitro- 

gen 

1.45 

1.36 

1.58 

.33 

.01 

+ .31 

B.  T.  U. 

14314 

13448 

14465 

1017 

875 

+ 142 

Table  6. 


( 


\ 


i 


f 


(,l  rTp  c r 


I 


i 


Balance  Sheet  for  Alberta  Coal 

Di-phenyl  Ether  Residue  to  Coal 


F 


Ash  Free 
Residue 

To  M & A 
Free  Coal 

Coal 

Differ- 

ence 

Amount  of 
Coal  to 
Extract 

[ 

Error 

Yield 

99.  5 

. 

.5 

Total  C 

80?  -31 

87.89 

88.30 

. 41 

.44 

-.03 

Sulphur 

.79 

.S9 

.81 

.03 

.04 

-.02 

Hydrogen 

4.96 

4.91 

4.69 

-.32 

.03 

-.24 

Oxygen 

4.39 

4.27 

4.55 

.18 

.02 

+ .16 

Nitrogen 

1.53 

1.51 

1.55 

.03 

.01 

-t.02 

B.  T.  U. 

15643 

15564 

1555  0 

'14 

77 

- 91 

Table  7 

/ 

Balance  Sheet  for  Alcoholic  Pota.sh  Residues-Illinois  Coal 


* 

Alcoholic  Potash  Residues  to  Di-phenyl  Ether  Residue 


Ash  Free 
Residue 

To  Ash 
Free  Di- 
phenyl 
Residues 

Di-pheny] 
Residue 
Ash  Free 

nffer-' 

ence 

Amt . 0 f 
Di-phenyl 
Res.‘ 
to  Ale*. 
KOH  Ext. 

Error 

Yield 

- 

92.91 

- 

- 

7.09 

- 

Total  C 

79.84 

74.17 

78.78 

4.  61 

5.57 

-.96 

Sulphur 

1.  44 

1.  34 

1.18 

'-.16 

.08 

-.34 

Hydroge 

1 4.98 

4.62 

6.28 

1.66 

. 44 

•1-1.22 

Oxygen 

13.50 

12.54 

12.10 

44 

. 86 

'1.30 

Nitrogen 

1.29 

1.20 

1,65 

.45 

.11 

+ . 34 

B.  T.  U. 

13728 

12754 

14269 

1515 

1011 

f 504 

Table  8. 

: 

Balance  Sheet  for  Alcdiholic  Potash  Residue-Indiana  Coal 
Alcoholic  Potash  Residues  to  Di-phenyl  Ether  Residue 


Ash  Free 
Residue 

« - « 
To  Ash 
Free  Di- 
phenyl Res 

— 

Di -phenyl 
Residue 
. Ash  Free 

Differ-' 
ence . 

Amt . of 
Di-pheny! 
Residue 
to  Alc.KOH 
Extract 

Error 

Yield 

98.2 

. 

1.8 

Total  C 

77.84 

76.43 

79.82 

3.39 

1.43 

4-  1.96 

Sulphur 

3.93 

3.84 

3.26 

' .58 

.06 

- .64 

Hydroger 

6.19 

6.08 

5.48 

- .60 

.09 

- .69 

Oxygen 

10.69 

10.49 

9.97 

-.52 

.17 

- .68 

Nitrogen 

1. 34 

1.31 

1.45 

.14 

.02 

+ .12 

B.  T.  U 

14492 

13631 

14314 

683 

258 

+ 425 

' Table  S, 

Balance  Sheet  for  Alcoholic  Potash  Residue- Alberta  Coal 
Alcoholic  Potash  Residues  to  Di-phenyl  Ether  Residue 


Ash  Free 
Residu  e 

To  Ash 
Free  Di- 
ph9n3’’l 
Residues 

Di -phenyl 
Residue 
Ash  Free 

Diff. 

= 

Amt . of 
Di -phenyl 
Residue 
to  Alc.KOH 
Ext  ract 

Error 

Yield 

- 

99.87 

- 

- 

.13 

- 

Total  C 

89.78 

89.66 

88.  31 

-1.35 

.115 

-1.46 

■^■^Iphur 

. 74 

.74 

.79 

.05 

.003 

+ .048 

gydrogen 

4.35 

4.  34 

4.96 

.63 

.005 

+ .615 

Oxygen 

4.Q5 

4.04 

4.  39 

.35 

.005 

+ .34  5 

N itrogen 

1.11 

1.11 

1.53 

.41 

.003 

+ .408 

B.  T.  U, 

15  444 

15433 

15643 

330 

30 

+ 200 

Table  10. 

, / 

0, 

Carbonization  Tests  of  Coals,  (10  Gr.  Sample  to  500  J.  | 

Illinois 

Indiana 

Alberta 

Water  (CaClJ 

. 426  fo 

.249% 

. 539% 

Water  and  Tar 

1.  77 fo 

2.0  5% 

. 41% 

Hydrogen  Sulfide 

.356% 

.906% 

none 

Coke  Left 

6.75% 

6.95% 

9.  40% 

Volume  of  Sas 

500  cc 

850  cc 

600  cc 

0 

0 

Formation  Temp,  of  H^^S 

410  C 

340  C 

- 

0 

0 

Formation  Temp,  of  Tar 

410  C 

- 

480  C 

Kind  of  Coke 

Weak 

Hard  Dense 

> 

Powder 

Table  11. 

^ -%<■«  Mu  m ■ /f, 


i* 


!fcvr  _ 


I 

1: 


r t 


©MVIw® 


T *“*  '\ 


jy.-. 


V I .'■.■'■'■■SI?  -'■* -'v  . 

>e? .,3f  ■,^''-«,  •■  6*i!i 


fik-«'J>  I 9ft i . ft*-  t^_i '•  * ' 

4m* — ^ 

' ' • ' ■-  ■ ^;K'  ‘ ■ ^^v■'i^i-:^;v:^■  :.. 


0 


a-jt 


0 

U ' Cp^ 


.0  C5^  1VH 

c ■ ' 


A 

i'*;' 


r-:^J  "/I 


ti:^  i i .it  *i»v  1 


-*  ■ * #1^  - -ii>  ^ «fc  0Hr  I u ' 

^ ^ 13  , 


L''^  -.-■  > ‘‘  ,',  ■ '.'.  'j'  .n 

•V.- ’A-iv"'*:  '.'*  . rfB-  'tZ,:'-.~  ,-!  ■ i. ’^,-''1  i>  , ;« 


yi<. '^...■irf,  ^ ■■/,.>..  ■‘‘’IS 


|l/ 
%«'.4 


it  "f 

l‘-  r..-.as*««r 


(i*  . * -.(jt-l’ 


f^,s;rac?B=v ' -ai^^itcs 


__  f . ■'  :•  N 
j*  j ,'  4'  .,''v---'«y  7 


Carbonization  Tests  of  Di-Phenyl  Residues 

5 Grs.  to  500  degree 

8 C. 

Illinois 

Indiana 

Alberta 

Water  (OaCl^) 

1 . 34f. 

.43fo 

Water  and  Tar 

1 — 1 

30^0 

8 . 4f. 

Hydrogen  Sulfide 

• 

CO 

• 

C5J 

CD 

none 

Coke  Left 

60< 

66  f. 

81  fo 

Volume  of  Gas 

10  5D  CO 

450  cc 

500  cc 

0 

0 

— 

Formation  Temp,  of  H^S 

445  C 

410  0 

0 

0 

0 

Formation  Te-ip.  of  Tar 

410  C 

315  C 

400  C 

Kind  of  Coke 

Powder 

Powder 

Powder 

Table  12. 

PiPr"' 

v:  s,:ii:^-  r T— ^:r'  WV’^''' 


ft 


:v‘<  i- 


r.afcr: 


■ '4^  V. 


• f*??*  ' 

-D 

^r  f:  . 'j- 


i-r'* 

t. --•  '\w 


■f' 


.mO.f,  V ^ 


. *^F*  n • ' "*  • 4 


M ui 


Vr  i'"''- ■;  ‘K^  ( ^OitS)) 

^^'6!  '•  I ^tfy»i.r«'ii»i  iiii»i>»»<W(>lp»ifii  4i~"  ' ''' 


. • 4' 

CO  C^<  i 


'■i.'i 

9fcit  R^3(7^tH 

.-T..  ^ •*'■ 


.'“■  * .< 


,1  V.V 


TO 


i''  0 ■-  [ ^ . 

i;  ' ' ■'  . . I 0 4X*,.  f O'-f.'^X-  ^,,H 

! 


■ ? w^. 


l"»’»‘. 


p$r  "*"  *»*i 


p ^£2^,  r p c^r>  kjof  a'&- ■9,'^ 

■*  .■».  ....^Mi  ^ . - I . . . . 


■w 

1)  . 


v« 

C, 


^ 'a' A 

.,!-v.v^  ^ 

♦v>.‘-  .Jh* 

•>x  •>  ' . ■^•:  4 

V -,-'B  V. ,.  V,  -^rj  y—  4 If' 


’ , '■  '*  t ' ' I 4' 

► > - i • Uf 

Vi'-f-!§<^’  ■"''^ 


'.‘7  ■r*^';<..)--jj..L 

r... '.'  : : 


Vs  1 


- i>\j 


a .1 

‘‘w  0 ' ■'  ■ I f A ■ ■■>>  y w~ ' 

O ^ .,.l|it*i'  ■ . J'‘„  • ’.^ 

wt.  '/A*;  ^ 


Carbonization  Tests  of  Alcoholic  Rotash  Residues 

0 

5 grs.  to  500  C. 


Illinois 

Indiana 

A1 berta 

Water  (CaClp.) 

1 1c 

1.S4  1 

1.78  1 

Water  and  Tar 

10  1 

16  1o 

00 

Hydrogen  Sulfide 

Hone 

.25  $ 

None 

Coke  Left 

CO 

73  1o 

CO 

CO 

Volume  of  Gas 

500  CO 

650  CO 

600  cc 

Formation  Tenp.  of  HS 

V 

0 

420  C 

Formation  Temp,  of  Tar 

410o  C 

0 

375  C 

0 ' 
410  C 

Kind  of  Coke 

. . 

Powder 

Powder 

Powder 

Table  13. 

- f ' f ' ;.— ■‘•'•\r''^«eag  s^r^T/'.w^'  ;■ 

te-’r^-^-ilSii V j ",  ^^.j)  '<  ’iT-  >r^  i i ■ 

i 'i  H|P!V  '■' 

-..If#-.  .', . i7,Tr',-teJ . ' . ■’«■_■•'?-£ 


t. 


'■•  *1 

''■  I 


i'  ' - . 

I I . ' 


■'.  ■ '^rr':-s.> . 

V 'Vi?,  TV 

. A,  .-■  * ^ :•  '.  V-frVif  . r';-  UJ 

■ a;J  ••  . ’-L' 


I • ' V* 

■•>  #■' 


F , 


-D? 


«VJC  c 


■ 


t ‘ H ‘‘V  rTrLOClX/ 

r ^1  i^  ' 

:-r*  . 


r Sa'  • '' 


o 


• V 


7 ' J)- 

-■  t: 


J1JI' 

'^"~l=y.'g'*'*  *?**»" " r»l<«#^liii^  ,il  r-w.^./^ 

rT4&  ■ ■ 


, .,^v 

< < V I 


hi  Hv.  i.  .,  /4.^  <•  ■ ■ .'  ,. 

• " ^ •*  - -•~>*’‘*'*»-  ■ I i»«jiiitii<4i  -nXi.^-^-w  ■ «iij^ii^,^..i..<i^i|^  -I  — in»«i»  iiiiwi(S.i»>t4U^fi'<iMty  ■ 


mi;  Vi 


V 


!! 


<a 


I 


‘^40-  ' 


■ ' - tir9*,Vi(d5c«p4^^  -4|; 


L ■ H'  ^ais  /‘-*yV-7VtJ^9ii(oo  jy 

1.  ‘"^:’bs 


' 1 . ti ' 


»4i 


vt> 


> 


il^V-ro  -‘iQ^T 

'X.  - -.  t 


..siJjjrT  B 

- - •■■^  • itiWmii— »'«|i’n»'  I i>i  I i|rgwiyi . -;:  /vr 


^ L ' Vp^’rfl 


. ..'  ■,<'1?.V,;;.  .Si-' 

• **iii  •' -f  iV II* 


r ll  ’U  ' ' '■  ' '■ 

. . . . ; .. lA- V'  ',7  7'- 

,.p 

“ ' I.-.  > . •■  1 ;.,  fC  ■'  & ■ ‘ ' 


fit-  v7  'A 


- 

Analysis  of  Gases  from  Carbonization  of  Coal 

Nitrogen  Free 

j 

1 

1 

1 

1 

i 

Percent  Gases 

Illinois 

Indiana 

Alberta 

Carbon  Dioxide 

16.8 

6.3 

11.0 

Oxygen 

15. a 

40.  4 

19.4 

Unsat.  Hydrocarbon 

3.8 

4.8 

3.3 

Aromat.  Hydrocarbon 

1.8 

1.  3 

.6 

Hydrogen 

10.  4 

7.0 

f= 

1 

CO 

1 — 1 

Carbon  Monoxide 

4.8 

4.14 

6.8 

Methane 

31.3 

CO 

• 

o 
1 — 1 

31.0 

Eth  \ne 

15.6 

35.  3 

-10.6 

Table  14. 

V 

••  r • 


1 


* '4«A 


Analysis  of  Oases  from  Carbonization  of  Diphenyl  Ether 
Residues,  Nitrogen  Free. 


Percent  Oases 

Illinois 

Indiana 

Alberta 

Carbon  Dioxide 

11.5 

8.8 

18.6 

Oxygen 

43.4 

CO 

• 

1 — 1 
to 

41.6 

Unsat.  Hydrocarbon 

1.6 

4.3 

3jk-l— . . . 

Armat.  Hydrocarbon 

1.1 

.9 

0 

Hydrogen 

11.5 

3.0 

33.  4 

Carbon  Monoxide 

8.1 

4.0 

3.0 

Methane 

33.8 

48.  3 

13.  3 

Table  15. 


Analysis  of  Gases  from  the  Carbonization  of 
Potash  Residues,  Nitrogen  Free 

Alcoholic 

Percent  Gases 

Illinois 

I nd  i ma 

Alberta 

Carbon  Dioxide 

21.4 

43.7 

27.8 

Oxygen 

42.3 

14.1 

24.6 

Unsat.  Hydrocarbon 

2.3 

3.2 

1.1 

Arma t . Hy  d ro  c arb  on 

1.1 

. 7 

0 

Hydrogen 

4.  3 

5.2 

16.2 

Carton  Monoxide 

2.3 

3.2 

2.5 

Methane 

26.3 

30.9 

27.8 

Table  16. 

1 f 

Volume  of  Gases  from  100  Grams  of  Coal,  Nitrogen  Free 


I 


cc  per  100  grs. 

Illinois 

Indi;ana 

A1  be  rta 

Carbon  Dioxide 

840 

530 

660 

Oxygen 

775 

3440 

1164 

Unsat.  Hydrocarbon 

193 

398 

134 

, - . Armat . Hy  dro c arb  on 

93 

109 

36 

Hydrogen 

531 

' 597 

1108 

C_arbpn  Monoxide 

340 

353 

1 4 

409 

Methane 

1561 

904 

1860 

Ethane 

775 

3169 

639 

Total  Volume 

5000 

8500 

6000 

Table  17, 


^ , 


‘ , s 


vc7^  Ito  C9«i0  OOiT  e)6t4p3^  ' 

, ,4'  ^\]  ‘ "■ 


:f  ■. 


.\ 


r "■<>^- 


r'S-'>r  » 


*^i^<ifl  * I 


« ' ' ■ ' 'A 


Ji 

^ i.  n 


[;y.’-i?! f 

. '*•»  I - Ifl^ 

■»9I„  -ijf-.:  .41 


:.ivt  ct.., 


iH.  . 


, ■ . - . , ■ '^it»'*'‘’'‘  -*r 

rr  • I f •'  t\  >b'-  "'  ^ , «»  ^ i 


'■'■  -t4>'  \'^^^^Sitlii■o^,> 


r •-  -t  *• 
if ; . 


f>v  ^ f’“*^ ',L^  ^.  ■-  J 

F3;/  f%' 

t ;, !' ^ ''ii'  ife 


etT ,,  : 


I.  ,4.  ^ 

I."  'i'^'pSr: 


, -'**-•►  44* 


®:  «*:oV.li'/i^  '*’- 


V'i 

• _/  '■'  ■'«  •■»' 


M 

! 1 


*^»  ' t>  I 


,>  "f  ,tf 


Volumes  of  Gases  from  100  grs.  of  Di-phenyl  Residues 
Nitrogen  Free 


CC  per  100  Grs. 

111  ino  is 

Indi^ana 

Alberta 

Carbon  Dioxide 

2430 

794 

1860 

Oxygen 

9120 

3860 

4160 

Unsat.  Hydrocarbon 

336 

378 

310 

Armat.  Hydrocarbon 

331 

81 

0 

Hydrogen 

2430 

180 

2240 

Carbon  Monoxide 

1700 

360 

200 

Methane 

47  73 

4367 

1Z3CL, 

Tdjtal  Volume 

21000 

9000 

10000 

Table  18. 


A.t, 


.'■■■  . . ■ ■ \T''%  >'  ■ 

Xv.'?i  y.x>  . ^73?.  001  M'rJ’  To 


> ! 


i/'. ., 


. i 

‘n 


{«/;  rEi>£ 


4 ’.'  ^i» 


j 


tl. 


I 


. 'CXO.,. 


^ev 

MHiM  -.  A.  . . 

■ 

. -5aR?^_ 


,'■  I*;-.' 

*■' ' i’fr 


J.'  w& 


"i-*-  ■'  -f<lkAite — - •«**  #**♦  vWi  W-UBR  .Am; 1 1 mnwyip  *£* 

. ■ ' ' !"'■'■  '"■ 

..  > >.-'_-06I,  ■>[ 


' - '\  *•«  "•••'-'  '>■•  . 

; I ‘ 1 'jfti'ioiCE- k6#»!j0  > 

-*T  •••••  •'>*,_  *•  •♦^•-•;  1 1#  <m>*  ipy  lib  «<it*  i *«*>- 


‘-^  i . 


i - .,'. 


"i  -» 


vO!' 


s 


' \it: 


‘5r: 


'.'"■  ;'T- 


,- ^>:  ' tm' 

“ 3 ■ ’ • 


^-■ 


'/%  '|s1b 

rotmr  ;,  ,|ir 


. • '7 

‘ .A  J r 


;..v» 


I . 


t- 


i .’*  • 

K V 


. A .-V 

, . .'•■’’■  3n-'n 

:>V.,.i  ^ 


j .S 


r 


V(  \ 

:i*vv'"*'- 


..  ■Ji 

■ . v>^l;A^;;'  ;i  , 

■ .: ' ' ■ ■ ■ if.  :lt-  '#!  i_-W  -ij 

• -,ic"  ,'d'  'V^-^i,  -t'  ...>i.«il«,»lW^  r‘^-ikii 


» *■ 


'i'  - 

r.  ^*  ■ 

* ? 


U.  r 


• » >f,  * 

s I* , . • |V  , 

‘ -V-  Ji  ^»*■• 

#■'’'.*5  Sfc  t'' 


.'it  -ardW  ■ ''■■■./I  • .,  V ’ ;-i 

':J 


■;  'V.;/ 


^y^JSTT>3^>- . 


3 ^ 


f.  '• 


— Y^T»«« 


,i. 

’i  ■ ' 'V  ’ 

s 


» '{,■ 


't  ■“ 


. V 


-■ 


(A'  L 


'■xs.  jutmutei- 

••  ,\|  "'  C \.  . ' . ■ ■ ■ ^.' 


Volume  of  Gases 

from  100  Grs.  Alcoholic  Potash  Residues 
Nitrogen  Free 

CC  uer  100  Grams 

Illinois 

Indiana 

Alberta 

Carbon  Dioxide 

3140 

55  50 

3 780 

Oxygen 

4330 

1830 

3460 

Unsat.  Hydrocarbon 

330 

416 

110 

A rm  at . Hy  dro  c ar  bo  n 

11  0 

91 

0 

Hydrogen 

430 

675 

1630 

Carbon  Monoxide 

330 

416 

350 

Methane 

3630 

4033 

3780 

Total  Volume 

10000 

13000 

10000 

Table  19. 

-10- 


IV.  Discussion  and  Conclusion. 

Di-phenyl  ether  will  remove  the  coking  property 
of  coal.  It,  however,  does  not  remove  all  of  the  resinic 
mattery  for  the  residue  will  give  tar  v/hen  carbonized  and  an 
extract  when  treated  with  alcoholic  potash.  For  two  of  the 
samples  the  ash  on  the  residue  is  practically  equally  to  the 
amount  of  the  ash  contained  in  the  original  coal.  This  indicates 
that  di-phenyl  ether  is  a true  solvent. 

The  residue  from  the  di-phenyl  ether  extraction  can 
be  handled  easily,  and  after  washing  with  ethyl  ether  it  can 

be  crushed,  to  a fine  powder  without  any  difficulty. 

19 

The  H:0  ratio  as  proposed  by  ??hite  for  a guide 
to  the  coking  power,  holds  true  in  all  the  carbonization  tests. 
The  Indiana  Coal  is  the  only  one  that  had  a hydrogen  tO' oxygen 
ratio  greater  than  59,  and  it  is  the  only  one  that  produced 
a good  coke.  ^ 

From  Table  1 it  can  be  seen  that  the  amount  of 
material  extracted  does  not  depend  upon  the  time  of  extraction 
to  any  great  extent.  Also,  it  is  not  necessary  to  keep  the 

solvent  It  its  boiling  point.  The  temperature,  however, 

o 

should  not  be  below  200  C. , because  under  such  conditions  the 
coal  will  Ccike  in  the  bottom  of  the  flask,  and  it  is  more 
difficult  to  filter  the  relative  coal  solution. 

The  volatile  matter  on  all  the  residues  is  higher 
than  on  the  original  coal.  This  iS  due  to  traces  of  the  sol- 
vent that  were  not  removed  in  washing  the  residues.  This  fact 


,r 


i 


V-  ..  f -I 


"I  . J 


»r^ljs;iii'ncvl.  fr*/:  rfOito^u^c  vM,.  > 


■H  .'.1 


\’^^^oovit  ?fc»jD4»  -f'?'^’  t<-4’»9  J'v5C»d«r-ifI  ;} 


»i'  »■ , 


rMt  «ri  6fW  r'tl»  7 .-^ofj  %tt  .LeoC'lo 

.'"'■  -,  \ tfl.  - j ' -. 


udi  \a  irt^  ^Xtml0ciJf‘  d/i# 

' " .,.  .«:--''-vjl(  !■  "U  V.-  '.'  /--: 


4' 


■f->‘''l  '>•  . ‘ I "it 

»ii-t  0^  ritj  >/r^  vtx^oi;toAt‘:  $jf  f«rfrt-a9x  •■ 

• "■■•<  tji  ^ ■ '••f  i 


^ -t  rlM  ' * 

aWT  tiv«  -U  .^mria^^iiPo  disiS 

'»■  ^ ^:T.'  ^ ij  V;^"  ' ' ' ' ' 


. « ,?v£p  9 J t * i,  t . 


- ')  KV' 

/lp|tDr7T3?s  WJtfflpt.  ’ 


'i^i' 


^ . \4 

■ F.  ' V .^i^  “ « 

. i'*;«oil'tii  m#  jwW‘>*^Te*wi}4  #irrt.  *;<(#' lisiiiM^W 

.1  ^ ^ . '■'  s’-  i*  ^ ' ' ■ ^ 


s-t^  fri  '■•crri  t ‘-XodV 


' ff9;<5yfo- 04^  . i«4  sn<?  vi^io  (si 

Spoolio-l^  iTk.t^  tiiSO  M£  Oitr**  ’ 


*Vi> 


’ . io  ’^n'.cpiluj:/  nilf 


-*■ 


..V' 


■ 


F-  ; 


np5»  >?Cf'  .f- 

':a  ac^  Apficiet  JPr'^«'-eab 

fe"'"  V.'  ' ■ ■ ‘ ' ■ ,E:^i 

" ■,t’!r56V:>i'piX  ..  cti, 

. ‘L'Y  ‘'  J- . ' 

■x-'j  i:ictj}'tun  ^om  r^’w  op^jlrotnii iL 

f,^7 

I'V  i”'',,-  ‘^.1  T ■ 

,,.  T^-^riX'ii:.  ajjitfi.  , fX4\rtb'^  ■£a.tf;f»;(r..'p,fi*ff-  r^sv- W? 


KS 


. / 


-—  J <i; 


-r£op  *!<?  ef0£  Vii  of-  Vil  W'tpft  '.Z^PpF^nijj.txo  «4i^:  ffo^a,^/f;r 


^-I’l  airf?'  . ^lii  tii  ;t:id^v|',* 


I .-'Ak  4l 


■ JflV"  J 


-11- 


isalso  shown  in  the  balance  sheets,  tables  5,  6 and  7,  in 

which  hydrogen  shows  an  increase  in  two  cases,  while  the 

ox3'-gen  has  increased  in  one.  The  increase  in  oxygen  could 

be  due  to  the  solvent  tSieat  had  been  left  in  the  residue  or 

18 

to  absorption  of  oxygen  from  the  air.  Cherry,  working  with 

phenol,  found  that  the  residue  shows  an  avidity  for  oxygen. 

The  alcoholic  potash  residues  show  a decrease 

in  volatile  matter  for  two  of  the  samples,  while  the  oxygen 

content  shows  an  increase  on  the  siune  samples.  The  difficulty 

in  using  alco’olic  potash  lies  in  the  fact  that  if  the  residue 

is  not  carefully  washed,  some  of  the  KOH  will  remain  in  the 

residue.  This  is  what  happened  with  the  Indiana  residue  where 

the  ash  on  the  original  coal  was  9.33  percent  and  34.99  percent 

on  the  alcoholic  potash  residue.  It  was  found  that  if  the 

residue  was  placed  in  a beaker  inrith  water  and  acid  added  until 

potash 

the  solution  v/as  neutral,  the  ash  on  the  alcoholic  residues 

will  be  very  close  to  the  values  on  the  original  coal. 

The  gases  from  the  carbonization  of  the  alcoholic 

potash  residues  show  increases  in  carbon  dioxide.  This 

increase  is  partially  due  to  oxidatioi  or  to  absorption  of  carbon 

dioxide  by  the  alkaline  solution.  Carbon  monoxide  is  lower 

on  the  alcoholic  potash  residues,  showing  that  part  of  it  mi^it 

have  been  converted  into  carbon  dioxide  during  the  extraction 

process.  The  carbon  dioxide  on  two  of  the  di-phenyl  ether 

residues  show  an  increase' and  one  shows  a decrease.  Parr 
17 

and  Hadley  said  that  any  increase  in  carbon  disxide  on  the 
residue  from  a phenol  extraction,  was  due  to  oxidation.  ; 


, i 


f.i.-.'i'  .‘3  ,, -^,t^ 


I‘d  8<^-  rri  ^ffnrc.le  6»Xi«ll 


^tt4wr  T(>f  fi  r?fc'  «iro£$tf  [j 


i3£jaoo  rri  erfT  *iJci/0  ai  b^a^%6n  I nhd  n^^ypic 


’< 


■ %o  m rreac^  bid  ^liSt  tjiX^  at  9t/Xi^d  n 


dflx{f  ,‘^'s9d0  ,t.L  jtdt  yo^  '119^^0^' 


r 


►’4 


'A.  t 


'’  .-^-'r^  --j 


Ti' 


■.  .■• 

k 


,\ 


'^a''^.zoab  s toa's  So?  if*'**}  s/Jh^A^oISif 


■ . f I' 


^ -TTM 


.^1 J -eXirfw  , 9$lngi^9  ^r(t  to  .;0t  ? -sEV 

• X ' ' V ' ' r ^ 

,afiIT  ■ . ' -^I']‘ft$B  m-,v  'ir.^  .08  swo^a  V- 

* '"  K-  t.  '; 

etft  tt  fpj)%  i ..  d«JF^o<3r 

■■  \ . '"  f’.'  r.-,  t ■'^'1  Hj5!  1 

84^  XLXr  TJO?  ^S(h^a  AinOr  ,:^ad9xfi  to^  e^L.  , ! 

' ■^  ,:v  - **■  ’??  ' 

r/ a ■:3-'fv»  eafc  i^a*!  nfJvXi'iil  bV  t al 

'’  . ’ >4?  ' r ' Bl  ^-:  ■:  II- t* 

• .-  • _ ^ '*  *-  .*  - /-  ■ ' 'v  ' . ‘ ■-*»,  If  .- -i! 

ts&i[>5eq  . r-£,  Jb/ifi  ^ae>o^eq  Xroo  fi^><Ti??Xtfo\©  dit  ^'o  rfoii  .4dtif  ,i  v 

' ' ^'  , ' . ■,  ■'it'''  ■'^  • TjJ,  ^|k' 

8/S:!^  r,>  v'df^  SaL'ot  ©aw  fl  d^sfa^  OiXodooXi;' 

'*!  ■ .'  , •',  |,ff.  "■  ■ 

It:^4»‘.  1;*%*^^*  bkai  trs  •Sr^/,'ntY<Ui^  TT^-^-tsK  i>  nX  jbeoi^Xq  §aw' 

’ *'''•  .-  ■ ' .i'  . ,1^ 


S9v  ls>^i  oiXA’orv-li-4'tfvJ‘  40  dar  v'lf  X/tJfi/©fr  6Airr«oXi-«Xoo' e^v 


^ i 


. XjpO^  X-iiiXj^t'ra  - .Tc  »oui/.  v sdt  at  oooXo  t^av  M IXlTr 


a ; 
A 


- it  , C'Mo^ooX®  oSl  "itv  (^Itfsi^^TyV  'Od^  xioit  'vi 


v<. 


ordT 


notf-T^-n  ri  wod« 'iiei;XjXa»*i  d6£to<s[ 

■iioifeiro  ?o  ;rroX  ^ -ic  .Ai  ^X-ju^itrcy  TfrXj£‘i^5i«'.q  af%W 


t d:.:.-  >f  :i^-.  'ii4q-  ,%cri?rodt  i&&:^bte9i  dt^Af  aq  o'JtladottCi'Je^iTjao^j  : 

. / ‘ ■ ' ' il;.^ 

y not^rcv-ttxa  9^  ejb^iyn£^  nocftfo  otfix  ^Jjayt^vitoo  ayji4-S  [[;-^ 


ccftcy:)  to  'pw-t -4<x?T«’o,  'A.'.aoipoicr^. 

a,  ■,.  ' ■ ■’  'ij'^  ■■  I,'  '::  v'  ■“■■';■■  '•>,[■*  ' ■ 

' ...  1'  ■ . . 'll  '.:^.-Aj  r '.  ® ,"'  .*.-  :■' 

^ *rtnr- t ,0i)»Tott9  «rto  Ott':4!^ib4X  m'*v^  WodO’'iia^<^ 

, •;  . >i'  . ^ ■ 'W 


40  c^d:$;pO  9€Fa*SiOrti  vft,’  ^ Jbid 

.‘loi  n-t  j84^*j  tj-CA -'ix©  Xcnnd^, » m'OTX- 


ki 


• • 


-12- 


Carbon  monoxide  decreases  on  the  coals  where  carbon  dioxide 

increases  and  increased  on  the  sample  that  showed  a decrease 

of  carbon  dioxide  on  the  di-phenyl  ether  residue.  According 

20 

to  Porter  and  Taylor  carbon  dioxide  and  carbon  monoxide  come 
from  cellulosic  materials,  so  it  would  be  naturcil  to  expect 
an  increase  on  the  residues  which  contain  a higher  percent  of 
cellulosic  material. 

V.  Summary. 

1.  The  products  of  Di-phenyl  ether  extraction  are 
in  such  a condition  that  they  can  be  easily  handled. 

2.  Time  over  six  hours  does  not  increase  the  amount 
of  extracted  material. 

3.  The  temperature  does  not  have  to  be  at  the  boilipg 

0 

point  of  di-phenyl  ether,  but  it  should  not  be  below  200  C. 

4.  The '3:e  si  due  8 from  both  di-phenyl  ether  and  alcoholic 
potash  extractions  show  an  avidity  for  oxygen. 

5.  It  is  impossible  to  remove  di-phenyl  ether  completely 
from  the  residue. 

6.  Di-phenyl  ether  does  not  remove  all  of  the  resinic 
matter,  but  it  leaves  a residue  that  will  not  coke. 

7.  The  ash  on  the  di-phenyl  residue  can  be  usually 
checked  back  to  the  value  orir  the  original  coal,  showing  that 
di-phenyl  ether  is  a true  solvent  of  the  coal  substance. 

8.  Di-phenyl  ether  is  a much  better  solvent  than 
either  phenol  or  pyridin,  because  it  is  easier  to  7;ork  with 
than  phenol  and  will  not  form  addition  products  as  pyridin 
will  do. 


* -t‘ 


..  <0 

’’■Of-I'i  f: 


: + a It 


' V 


/ ' ” > i ■ 

r 4 ^ 04  * \ 


•\  r-  r 


I fine’  ot'f 


,T:i^ 

' '.  J 


-13- 


9,  The  use  of  alcoholic  potash  is  not  as 

advant eous  as  that  of  di-phSnyl  ether,  because  it  is  very 
easy  for  the  residue  to  absorb  carbon  dioxide,  and  the 
residue  must  be  I'^c^shed  very  carefully  in  order  to  remove  all 
of  the  alcoholic  potash. 


_ ' ry  .>11 


V ^ . i'"' "'' 

,,  , . * . , *■  V.  /.'•  ^ i ■','  ,*'  ' . ■'/  ' 

r ■ '^  ' 


'yi^lU  !iT.'»3r%7  o vni^to  iJfMe<»v  v^ao 

.0  ■ ■ ■^-m-S  >'  ’ ' J,;  '■■  w‘-i 

K,  . .,  ‘".iriyi  ->'  I ‘ ■ ' . f 


It' 


. . u 0/‘  (to'qr  oi  I o4o^r o 


.. . . 

' ' I . ■ ■ '<J 


'i:  - K ■'  ‘.V4.) 
^ ' ■■:  M ' 

A J '^'^■’ 


i'W-  F 


11..'''*%'  .<H^' 


•di.  V 

if*  i 


« * 


"V  ' 


.•'  L 

» r /•  ^ 


■ ?il  V’ 

• *.’l-  *'  ^ : ■») 

■ /Im'  rf*^  ^ ■''.  • <n* 


C,  !5  ■ ■ .^ii7 

.•.•.‘:V  v^.»'jiia'':v  ti;«j 

. - ■ ■f 


-13- 


VI.  Bibliography 

1.  Bulletin  #82,  U.S.G.S. 

Bulletin  #38,  Bureau  of  Mines 

2.  Thesis,  University  of  Illinois,  1921. 

3.  Bulletin,  University  of  Illinois,  Engineering  Experiment 

Station,  No.  111. 

4.  Jour.  Chem.  Soc.  Vol.  48,  page  876. 

5.  Jour.  Soc.  Chem.  Ind.  1898,  page  1013. 

0,  M ti  11  11  Vol.  20,  page  789. 

7^  11  11  II  « ” 21,  page  242 

S,  II  II  « ” ” 27,  page  150 

9.  Progressive  Age.  Vol.  29,  page  1030. 

10.  Annalen.  Vol.  399,  page  120. 

11.  Berichte,  Vol.  44,  page  2486. 

12.  Compt . Rendus.  Vol. 158,  page  1421. 

13.  Berichte,  Vol.  49,  page  1460. 

14.  Comt.  Rendus:  Vol.  ’ 154,  page  1094. 

Bulletin  Soc.  Chem.  Vol.  21,  page  78. 

15.  Jour.  Oh:pm.  Soc.,  Vol.  103,  p?ge_  1704. 

16.  Tech.  Pa.per,  Bureau  of  Mines,  No.  5. 

17.  Bulletin  Univ.  of  111.  Eng.  Expt.  Stat.  No.  76. 

18.  Thesis  University  of  Illinois,  1920. 

19.  Bulletin,  Bureau  of  Mines,  No.  29,  1911. 

20.  Technical  Paper  140,  Department  of  the  Interior. 


